Reshapable hair styling composition comprising (meth)acrylic copolymers of four or more monomers

ABSTRACT

A reshapable hair styling composition comprising at least one (meth)acrylic copolymer comprising: (a) units derived from at least one monomer chosen from (meth)acrylate esters of branched and straight chain alkyl alcohols, (b) units derived from at least one monomer chosen from (meth)acrylate esters of saturated and unsaturated cyclic alcohols containing 6 to 20 carbon atoms, (c) optionally units derived from at least one monomer chosen from hydrophilic monomers, and (d) optionally units derived from at least one monomer other than (a), (b), and (c) monomers, wherein said at least one (meth)acrylic copolymer comprises units derived from at least four different monomers and wherein said composition provides a reshapable effect.

The present invention relates to a reshapable hair styling composition.

Fixing the hairstyle is an important element in hair styling, andinvolves maintaining a shaping that has already been carried out, orsimultaneously shaping and fixing the hair.

In accordance with the invention, the term “hair styling composition”relates to any kind of hair composition that can be used to effect hairstyling, for example fixing compositions, shampoos, conditioners,permanent waving compositions, hair care products, and hair treatmentproducts.

The most prevalent hair styling compositions on the cosmetic market forshaping and/or maintaining the hairstyle are spray compositionscomprising a solution, usually alcohol- or water-based, and one or morematerials, generally polymer resins. One of the functions of polymerresins is to form links between the hairs, these materials also beingcalled fixatives, in a mixture with various cosmetic adjuvants. Thissolution is generally packaged either in an appropriate aerosolcontainer, which is pressurized with the aid of a propellant, or in apump flask.

Some other known hair styling compositions include styling gels andmousses, which are generally applied to the wetted hair before brushingor setting it. In contrast to the conventional aerosol lacquers, sometypes of these other known hair styling compositions disadvantageouslyare not designed to allow the hair to be fixed in a shape created beforetheir application. In fact, these compositions are essentially aqueousand their application wets the hair; hence these compositions are notdesigned to maintain the initial shape of the hairstyle. In order toshape and fix the hairstyle, therefore, it is necessary to carry outsubsequent brushing and/or drying with these types of compositions.

Thus, many hair styling compositions exist that have the samedisadvantage: they are not designed to allow the hairstyle to be latermodified to a desired shape, which is other than that formed initially,without starting the styling and fixing operations again. Moreover,under various kinds of stress, the hairstyle has a tendency to take onan undesirable permanent set, which cannot easily be modified. Also inthe styling process, one desires hair conditioning benefits, such asease of combing and soft hair feel appearance.

A subject of the invention is a reshapable hair styling compositioncomprising at least one (meth)acrylic copolymer comprising: (a) optionalunits derived from at least one monomer chosen from (meth)acrylateesters of branched and straight chain alkyl alcohols, (b) optional unitsderived from at least one monomer chosen from (meth)acrylate esters ofsaturated and unsaturated cyclic alcohols containing 6 to 20 carbonatoms, (c) optional units derived from at least one monomer chosen fromhydrophilic monomers, or (d) optional units derived from at least onemonomer other than said (a), (b), and (c) monomers, wherein said atleast one (meth)acrylic copolymer comprises units derived from at leastfour different monomers, wherein said at least one (meth)acryliccopolymer comprises at least one unit derived from monomers recited ineither (a) or (b), and wherein said composition provides a reshapableeffect.

Another subject of the invention is a reshapable hair stylingcomposition comprising at least one (meth)acrylic copolymer comprising:(a) units derived from at least one monomer chosen from (meth)acrylateesters of branched and straight chain alkyl alcohols, (b) units derivedfrom at least one monomer chosen from (meth)acrylate esters of saturatedand unsaturated cyclic alcohols containing 6 to 20 carbon atoms, (c)optional units derived from at least one monomer chosen from hydrophilicmonomers, and (d) optional units derived from at least one monomer otherthan said (a), (b), and (c) monomers, wherein said at least one(meth)acrylic copolymer comprises units derived from at least fourdifferent monomers and wherein said composition provides a reshapableeffect.

Another subject of the invention is a reshapable hair stylingcomposition comprising at least one (meth)acrylic copolymer comprising:(a) from about 10 to about 85 weight percent of units derived from atleast one monomer chosen from (meth)acrylate esters of branched andstraight chain alkyl alcohols, (b) from about 5 to about 70 weightpercent of units derived from at least one monomer chosen from(meth)acrylate esters of saturated and unsaturated cyclic alcoholscontaining 6 to 20 carbon atoms, (c) from 0 to about 20 weight percentof units derived from at least one monomer chosen from hydrophilicmonomers, and (d) from 0 to about 20 weight percent of units derivedfrom at least one monomer other than said (a), (b), and (c) monomers,wherein said at least one (meth)acrylic copolymer comprises unitsderived from at least four different monomers and wherein saidcomposition provides a reshapable effect.

Another subject of the invention is a reshapable hair stylingcomposition comprising at least one (meth)acrylic copolymer comprising:(a) from about 20 to about 80 weight percent of units derived from ethylhexyl (meth)acrylate, (b) from about 5 to about 65 weight percent ofunits derived from isobornyl (meth)acrylate, (c) from about 1 to about15 weight percent of units derived from acrylic acid, and (d) from about1 to about 15 weight percent of units derived from methacrylic acid,wherein the ratio of ethyl hexyl (meth)acrylate derived units toisobornyl acrylate derived units ranges from about 0.5:1 to about 6:1,wherein said composition provides a reshapable effect.

The weight percentages of the (a), (b), (c), and (d) units may be basedon the total weight of each monomer type used compared to the totalweight of all monomers used.

Another subject of the invention is a reshapable hair stylingcomposition comprising at least one (meth)acrylic copolymer, asdescribed above, wherein said reshapable hair styling composition is inthe form of a spray, aerosol, mousse, gel, stick, mud, or lotion.

Another subject of the invention is an aerosol device comprising avessel, which comprises: (1) an aerosol composition, which provides areshapable effect and comprises a liquid phase comprising at least onecomposition comprising at least one (meth)acrylic copolymer, asdescribed above, and a propellant, and (2) a dispenser.

Another subject of the invention is a method of cosmetically treatinghair, comprising applying to the hair before, during, or after shapingof a hairstyle of said hair a composition comprising at least one(meth)acrylic copolymer, as described above, wherein said compositionprovides a reshapable effect.

Another subject of the invention is a method of reshaping hair,comprising: (1) applying to the hair before, during, or after theinitial shaping of the hairstyle a composition comprising at least one(meth)acrylic copolymer, as described above, wherein said compositionprovides a reshapable effect, and (2) thereafter shaping the hairstyleat least once, wherein no additional composition or heat is added.

Another subject of the invention is a method of manufacturing areshapable hair styling composition comprising including in a hairstyling composition at least one (meth)acrylic copolymer, as describedabove, wherein said at least one (meth)acrylic copolymer is present inan amount effective to provide a reshapable effect.

In one embodiment of the invention, such reshapable hair stylingcompositions may be in the form of an aqueous emulsion or dispersion.All emulsions comprise a continuous phase and at least one dispersedphase. The term “dispersion” means generally a multi-phase system whereat least one phase contains discrete particles distributed throughout abulk substance. A portion of the copolymer may exist as the discreteparticle in an aqueous phase. Dispersions are possible through the useof certain components that are insoluble in the aqueous system. By“dispersion,” it is also meant that not necessarily the entire copolymerneeds to be water insoluble; some of the copolymer can be soluble in theaqueous mixture. It may be desirable that a dispersion remains stableunder ambient conditions. In one embodiment, dispersions are stable atroom temperature for more than 30 days, such as for more than 90 days,for more than 180 days, and for more than 360 days. A dispersion isdeemed stable so long as the discrete particles of the internal phaseremain distributed throughout the bulk substance (external phase).

In one embodiment, such dispersions may be blended with otherdispersions or with other known additives such as fillers, plasticizers,pigments (such as carbon black), silica sols and other known levelingagents, wetting agents, antifoaming agents, and stabilizers.

The term “(meth)acrylate” is used to encompass both of the termsacrylate and methacrylate. Similarly, the term “(meth)acrylic acid” isused to encompass both of the terms acrylic acid and methacrylic acid.

The term “reshapable” hair styling composition means a hair stylingcomposition providing hair styling that can be restored or modifiedwithout new material or heat being applied. For example, in order torestore or modify the hairstyle in case of “drooping” or loss of setting(dishevelment), no new materials, such as water or any form of fixingagent, or heat are required. Thus, to provide a “reshapable” effectmeans to provide a hair styling that can be restored or modified withoutnew material or heat being applied. The efficacy of the composition canbe long lasting, such as 10-24 hours, giving rise to a durable stylingeffect. Other terms, which may be synonymous with reshapable, includerepositionable, remoldable, restyleable, rearrangable, and remodelable.

In general, the monomers recited in (a) constitute, for example, fromabout 10 to about 85 weight percent of the total amount of monomersused. In one embodiment, they may constitute from about 20 to about 80weight percent of the total amount of monomers used. The monomersrecited in (a) may be chosen, for example, from (meth)acrylate esters ofC₁ to C₃₀ branched and straight chain alkyl alcohols, such as from(meth)acrylate esters of C₄ to C₁₈ branched and straight chain alkylalcohols. In one embodiment, the monomers recited in (a) may be chosenfrom isooctyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl(meth)acrylate, t-butyl (meth)acrylate, 2-methylbutyl (meth)acrylate,2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isononyl(meth)acrylate, lauryl (meth)acrylate, octadecyl (meth)acrylate, andmixtures thereof. In another embodiment, the monomers recited in (a) maybe chosen from 2-ethylhexyl (meth)acrylate, n-butyl (meth)acrylate,isooctyl (meth)acrylate, 2-methylbutyl (meth)acrylate, and mixturesthereof.

The monomers recited in (b) generally have a higher T_(g) than themonomers recited in (a). In general, they may constitute, for example,from about 5 to about 70 weight percent of the total amount of monomersused. In one embodiment, they may constitute from about 10 to about 70weight percent of the total amount of monomers used. In anotherembodiment, they may constitute from about 5 to about 65 weight percentof the total amount of monomers used. The monomers recited in (b) may bechosen from (meth)acrylate esters of saturated and unsaturated cyclicalcohols containing 6 to 20 carbon atoms. In one embodiment, themonomers recited in (b) are chosen from monofunctional (meth)acrylateesters of bridged cycloalkyl alcohols, having 6 to 20 carbon atoms, andaromatic alcohols. The cycloalkyl and aromatic groups may be substitutedby groups chosen from C₁ to C₆ alkyl, halogen, cyano groups, and thelike. In another embodiment, the monomers recited in (b) are chosen frombicyclo[2.2.1]heptyl (meth)acrylate; adamantyl (meth)acrylate;3,5-dimethyladamantyl (meth)acrylate; isobornyl (meth)acrylate; tolyl(meth)acrylate; phenyl (meth)acrylate; t-butylphenyl (meth)acrylate;2-napthyl (meth)acrylate; benzyl (meth)acrylate; cyclohexyl(meth)acrylate; menthyl (meth)acrylate; 3,3,5-trimethylcyclohexyl(meth)acrylate; dicyclopentenyl (meth)acrylate;2(dicyclopentenyloxy)ethyl (meth)acrylate; and mixtures thereof.

The optional monomers recited in (c) are hydrophilic monomers. Ingeneral, they may constitute, for example, from 0 to about 20 weightpercent of the total amount of monomers used. In one embodiment, theymay constitute from about 1 to about 15 weight percent of the totalamount of monomers used. In another embodiment, they may constitute fromabout 1 to about 10 weight percent of the total amount of monomers used.In one embodiment, the monomers recited in (c) may be chosen from thosemonomers having hydroxyl, ether, amide, amine, carboxylic acid, sulfonicacid, and phosphonic acid functionalities. In another embodiment, themonomers recited in (c) may be chosen from (meth)acrylamide,2-ethoxyethyl (meth)acrylate, mono (meth)acrylates of polyethyleneglycol monoethers, N-vinyl-2-pyrrolidone, N-vinyl formamide, N-vinylacetamide, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate,vinyl pyridine, N,N-diethylaminoethyl (meth)acrylate,N,N-dimethylaminoethyl (meth)acrylate, N-t-butylaminoethyl(meth)acrylate, acrylic acid, methacrylic acid, itaconic acid, maleicacid, fumaric acid, vinyl benzoic acid, 2-carboxyethyl (meth)acrylate,2-sulfoethyl (meth)acrylate, and 4-vinyl phenyl phosphonic acid. In yetanother embodiment, the monomers recited in (c) may be chosen from(meth)acrylic acid and N-vinyl-2-pyrrolidone.

The at least one (meth)acrylic copolymer may optionally include unitsderived from other monomers to improve performance, reduce cost, or forother purposes, provided that such monomers are used in an amount thatdoes not compromise the composition's reshapable effect. In general, theoptional monomers recited in (d) may constitute, for example, from 0 toabout 20 weight percent of the total amount of monomers used. Examplesof such other monomers may include vinyl esters, vinyl chlorides,vinylidene chlorides, styrenes, (meth)acrylate esters of C₁ to C₃ alkylalcohols, macromolecular monomers such as monoacrylic functionalpolystyrene and polydimethylsiloxane, and the like.

The composition may further comprise a cosmetically acceptable vehicle.The choice of vehicle is adapted to the method of application selected.The cosmetic vehicle appropriate for hair may be chosen from water,water miscible solvents such as lower alcohols, e.g., C₁ to C₄ branchedand straight chain aliphatic alcohols, and combinations thereof. In oneembodiment, the vehicle is a lower alcohol chosen from ethanol,n-propanol, and 2-propanol (IPA). When water miscible solvents and waterare present, the solvent to water ratio may range from about 20:80 toabout 90:10 weight/weight, such as from about 30:70 to about 85:15.

The vehicle may also comprise additional solvents. For example, otherrapid evaporating solvents may be used, such as hexamethyldisiloxane(HMDS); cyclic silicones (D₄ and D₅); C₄-C₁₀ alkanes includingisoparafins such as Permethyl 97A and Isopar C; acetone;hydrofluoroethers (HFEs) and the like.

The composition may also comprise additives such as gelling agents,foaming agents, and silicones. It is understood that the person skilledin the art will know how to choose the additional constituents and theiramount in the composition according to the invention, such as theconstituents of the composition, so as not to adversely affect orsubstantially affect its reshapable hair styling properties.

The inventive copolymers of the present invention may be prepared usingemulsion polymerization, solution polymerization followed by aninversion step, and suspension polymerization. These methods useinitiators that, through various techniques, are decomposed to form freeradicals. Once in their radical form, the initiators react with themonomers, starting the polymerization process. The initiators are oftencalled “free radical initiators.” Various decomposition methods for theinitiators are discussed first, followed by a description of theemulsion, solution, and suspension polymerization methods.

The initiator can be decomposed homolytically to form free radicals.Homolytic decomposition of the initiator can be induced by using heatenergy (thermolysis), using light energy (photolysis), and/or usingappropriate catalysts. Light energy can be supplied by means of visibleor ultraviolet sources, including low intensity fluorescent black lightlamps, medium pressure mercury arc lamps, and germicidal mercury lamps.

Catalyst induced homolytic decomposition of the initiator typicallyinvolves an electron transfer mechanism, resulting in areduction-oxidation (redox) reaction. This redox method of initiation isdescribed in Elias, Chapter 20 (detailed below). Initiators such aspersulfates, peroxides, and hydroperoxides are more susceptible to thistype of decomposition. Useful catalysts include, but are not limited to(1) amines, (2) metal ions used in combination with peroxide orhydroperoxide initiators, and (3) bisulfite or mercapto-based compoundsused in combination with persulfate initiators.

Presently, in certain embodiments of the invention, the method ofinitiation comprises thermolysis or catalysis. Thermolysis can provideease of control of the reaction rate and exotherm.

Useful initiators are described in Chapters 20 & 21 Macromolecules, Vol.2, 2nd Ed., H. G. Elias, Plenum Press, 1984, New York, the disclosure ofwhich related to initiators is specifically incorporated herein byreference. Useful thermal initiators include, but are not limited to,the following: (1) azo compounds such as 2,2-azo-bis-(isobutyronitrile),dimethyl 2,2′-azo-bis-isobutyrate, azo-bis-(diphenyl methane), and4-4′-azo-bis-(4-cyanopentanoic acid); (2) peroxides such as benzoylperoxide, cumyl peroxide, tert-butyl peroxide, cyclohexanone peroxide,glutaric acid peroxide, lauroyl peroxide, and methyl ethyl ketoneperoxide; (3) hydrogen peroxide and hydroperoxides such as tert-butylhydroperoxide and cumene hydroperoxide; (4) peracids such as peraceticacid and perbenzoic acid; potassium persulfate; ammonium persulfate; and(5) peresters such as diisopropyl percarbonate.

Useful photochemical initiators include but are not limited to benzoinethers such as diethoxyacetophenone, oximino-ketones, acylphosphineoxides, diaryl ketones such as benzophenone and 2-isopropylthioxanthone, benzil and quinone derivatives, and 3-ketocoumarins asdescribed by S. P. Pappas, J. Rad. Cur., July 1987, p.6, the disclosureof which related to photochemical initiators is specificallyincorporated herein by reference.

In one embodiment, the copolymers of the present invention can be madeby emulsion polymerization, generally comprising a process where themonomers are dispersed in a continuous phase (typically water) with theaid of an emulsifier and polymerized with the free-radical initiators,described above. Other components that are often used in this processinclude stabilizers (e.g., copolymerizable surfactants), chain transferagents for minimizing and/or controlling the copolymer molecular weight,and catalysts. The product of this type of polymerization is typically acolloidal dispersion of the copolymer particles, often referred to as a“latex.” In one embodiment of an emulsion polymerization process, aredox chemistry catalyst, such as sodium metabisulfite, used incombination with potassium persulfate initiator and ferrous sulfateheptahydrate, is used to start the polymerization at or near roomtemperature. Typically, the copolymer particle size is less than onemicrometer, such as less than 0.5 micrometer.

Emulsion polymerization can be carried out in several differentprocesses. For example, in a batch process the components are chargedinto the reactor at or near the beginning. In a semi-continuous process,a portion of the monomer composition is initially polymerized to form a“seed” and the remaining monomer composition is metered in and reactedover an extended time. These emulsion polymerization techniques are wellknown by those skilled in the art and are widely used in industry.

In another embodiment, the copolymers of the present invention can bemade by solution polymerization followed by an inversion step. In oneillustrative solution polymerization method, the monomers and suitableinert solvents are charged into a reaction vessel. The monomers and theresultant copolymers are soluble in the solvent. After the monomers arecharged, an initiator, such as a thermal free radical initiator, isadded. The vessel is purged with nitrogen to create an inert atmosphere.The reaction is allowed to proceed, typically using elevatedtemperatures, to achieve a desired conversion of the monomers to thecopolymer. In solution polymerization, the initiator used may comprise athermally decomposed azo or peroxide compound for reasons of solubilityand control of the reaction rate.

Suitable solvents for solution polymerizations include but are notlimited to (1) esters such as ethyl acetate and butyl acetate; (2)ketones such as methyl ethyl ketone and acetone; (3) alcohols such asmethanol and ethanol; (4) aliphatic and aromatic hydrocarbons; and (5)mixtures thereof. The solvent may be any substance which is liquid in atemperature range of about −10 ° C. to about 50° C., does not interferewith the energy source or catalyst used to dissociate the initiator toform free radicals, is inert to the reactants and product, and will nototherwise adversely affect the reaction. The amount of solvent, whenused, is generally about 30 to about 80 percent by weight based on thetotal weight of the reactants and solvent. For example, the amount ofsolvent ranges from about 40 weight percent to about 65 weight percent,based upon the total weight of the reactants and solvent, to yield fastreaction times.

Copolymers prepared by solution polymerization can be inverted to yielddispersions of small average particle size, typically less than aboutone micrometer, such as less than about 0.5 micrometer. Inversion ofcopolymers can occur in an aqueous carrier or aqueous solvent providedthat (1) they contain ionic functionality or (2) they contain acidic orbasic functionality, which on neutralization yields ionic functionality.

Copolymers containing acidic functionality are obtained bycopolymerizing acidic monomers. Suitable acidic monomers include thosecontaining carboxylic acid functionality such as acrylic acid,methacrylic acid, itaconic acid, etc.; those containing sulfonic acidfunctionality such as 2-sulfoethyl methacrylate; and those containingphosphonic acid functionality. Preferred acidic monomers include acrylicacid and methacrylic acid.

Copolymers containing basic functionality are obtained by copolymerizingbasic monomers. Suitable basic monomers include those containing aminefunctionality such as vinyl pyridine; N,N-diethylaminoethyl(meth)acrylate; N,N-dimethylaminoethyl (meth)acrylate; andN-t-butylaminoethyl (meth)acrylate. Examples of basic monomers areN,N-dimethylaminoethyl (meth)acrylates.

The copolymer may be prepared in a water-miscible solvent, which has aboiling point below 100° C., such as acetone or methyl ethyl ketone.Alternatively, a non-water-miscible polymerization solvent such as ethylacetate may be used. The non-water-miscible polymerization solvent maybe removed from the copolymer by using a rotary evaporator. Theresulting copolymer can then be dissolved in a water-miscible solventsuch as those described above or mixtures including isopropanol,methanol, ethanol, and tetrahydrofuran.

The resulting solutions are added with stirring to an aqueous solutionof a base (in the case of copolymers containing the acidicfunctionality) or an acid (in the case of copolymers containing thebasic functionality). Alternatively, the base or acid can be added tothe polymer solution prior to adding water or being added to water.Suitable bases include (1) ammonia and organic amines, such asaminomethyl propanol, triethyl amine, triethanol amine, methyl amine,and morpholine, and (2) metal hydroxides, oxides, and carbonates, etc.Suitable acids include (1) carboxylic acids such as acetic acid, and (2)mineral acids, such as HCl. In the case of a volatile weak base (e.g.,ammonia) or acid (e.g., acetic acid), the ionic group formed (anammonium carboxylate) is non-permanent in nature. For example, for a(meth)acrylic acid containing copolymer neutralized with aqueousammonia, the copolymer remains as the ammonium acrylate derivative whendispersed in water, but is thought to revert to its original free acidstate as the coating dries on the surface. This is because there isequilibrium between the neutralized and free acid, which is shiftedtowards the free acid as the ammonia is driven off on drying.

In yet another embodiment, the copolymers of the present invention canbe made by a suspension polymerization method. The suspensionpolymerization method for making the inventive copolymers can proceed inthe absence of surfactants. Instead, colloidal silica in combinationwith a promoter may be used as the stabilizer. Using this process,surfactant-free copolymers can be obtained with a relatively narrowparticle size distribution (such as, no greater than about 20%).

In one embodiment, the method for suspension polymerization involvesmaking a monomer premix comprising the (a), (b), (c), and (d) monomers.The premix is combined with a water phase, such as deionized water,containing colloidal silica and a promoter. Amphiphilic polymersrepresent one class of useful promoters.

The pH of the mixture is adjusted so as to be in the range of 3 to 11,such as in the range of 4 to 6, without coagulation of the particles.For certain monomers, the initial pH of the mixture can be as low asabout 2.5. This pH is low enough for the colloidal silica to stabilizethe monomer droplet, but the final product may contain a small amount ofcoagulum. Similar observations can be made at high pH. It has beenobserved that when the mixture is treated with ammonia or hydrochloricacid to a pH ranging from about 4 to about 6, the reaction is morestable and the final product is basically free of coagulum.

The mixture is exposed to high shear, such as that capable in a Waring™blender, to break the monomer droplets down to a diameter size of 1micrometer or less. The shearing action is then reduced to a loweragitation (or temporarily stopped) to allow for the partial coalescenceof the small droplets and formation of a suspension. Initiator is added.The silica-promoter mixture stabilizes the droplets and limits theircoalescence yielding very uniform, and sometimes nearly monodisperseparticles. The suspension polymerization is completed under moderateagitation and a stable, aqueous dispersion of (meth)acrylic particles isobtained.

The above described suspension polymerization has several advantages.For example, the method yields a copolymer with a narrow distribution ofmean particle size and limited coalescence. When coalescence is present,the particles tend to migrate towards one another and can form largemasses. Coalescence hampers the handling and transportation of theparticles and thus is undesirable. The particles may be stericallystabilized by the colloidal silica.

Also, the method allows for copolymers that withstand freezingtemperatures, allowing them to be redispersed after thawing. It has beendiscovered that the copolymer is stable, i.e., does not coalesce whenthe same volume of alcohol (methanol or isopropanol) and water is usedin the dispersion.

In yet another embodiment of the invention, the (meth)acrylic copolymerhas a glass transition temperature (Tg) ranging from about −100° C. toabout 15° C. According to the present invention, the Tg of the(meth)acrylic copolymer is obtained following the application of the(meth)acrylic copolymer in a simplex vehicle to a substrate and thendrying. The glass transition temperature is determined by theDifferential Scanning Calorimetric method (DSC).

In one embodiment of the invention, the (meth)acrylic copolymer may bepresent in an amount ranging from about 0.1 to about 40, such as fromabout 0.5 to about 15, weight percent of the total weight of thecomposition in order to provide a reshapable effect.

The composition according to the invention may comprise one or moreother constituents, which are conventional in cosmetics, chosen frompreservatives; perfumes; active haircare agents; plasticizers; anionic,cationic, amphoteric (such as zwitterionic), and nonionic surfactants;hair conditioning agents such as silicone fluids, fatty esters, fattyalcohol, long chain hydrocarbons, emollients, lubricants, and penetrantssuch as lanolin compounds, protein hydrolysates, and other proteinderivatives; anionic, cationic, amphoteric (such as zwitterionic), andnonionic polymers; dyes; tints; bleaches; reducing agents; pH adjustingagents; sunscreens (such as UV filters); and thickening agents.

In one embodiment, the one or more constituents are chosen frompolymeric adhesives, for example fixing polymers, such as anionic,cationic, amphoteric (such as zwitterionic) and nonionic fixing polymersand combinations thereof. As used herein, the term “polymer” refers tohomopolymers and copolymers, which are derived from more than one typeof monomer, such as from two, three, four, or more different monomertypes.

The cationic fixing polymers comprise cationic moieties or moieties thatare convertible to cationic moieties. Suitable examples of cationicfixing polymers, which can be used according to the present invention,are those that may be chosen from polymers comprising at least one groupchosen from primary amine groups, secondary amine groups, tertiary aminegroups, and quaternary amine groups, wherein the at least one groupforms part of the polymer chain or is linked directly to it, having aweight average molecular weight ranging from about 500 to about5,000,000, such as from about 100 to about 3,000,000.

Among these polymers, mention may be made more particularly of thefollowing cationic fixing polymers:

(1) homopolymers and copolymers derived from monomers chosen from(meth)acrylic esters and (meth)acrylic amides comprising units of atleast one of the following formulae:

in which each R₃ is independently chosen from hydrogen and CH₃ groups;each A is independently chosen from linear and branched alkyl groupscomprising 1 to 6 carbon atoms and hydroxyalkyl groups comprising 1 to 4carbon atoms; each R₄, R₅, and R₆ is independently chosen from alkylgroups comprising 1 to 18 carbon atoms and benzyl radicals; each R₁ andR₂ is independently chosen from hydrogen and alkyl groups comprising 1to 6 carbon atoms; and each X⁻ is independently chosen from methylsulphate anions and halide anions, such as chloride or bromide anions.

In one embodiment, the copolymers of family (1) further comprise atleast one unit derived from monomers chosen from (meth)acrylamides,diacetone (meth)acrylamides, (meth)acrylamides substituted on thenitrogen by a group chosen from lower alkyls, (meth)acrylic acids,esters of (meth)acrylic acids, vinyllactams such as vinylpyrrolidone andvinyl-caprolactam, and vinyl esters.

Thus, mention may be made, among these cationic copolymers of the family(1), of:

copolymers of acrylamide and of dimethylaminoethyl methacrylatequaternized with dimethyl sulfate or with a dimethyl halide, such asthat sold under the name Hercofloc by the company Hercules;

copolymers of acrylamide and of methacryloyloxyethyltrimethylammoniumchloride which are disclosed, for example, in EP-A-080,976, thedisclosure of which relating to cationic polymers is incorporated hereinby reference, and sold, for example, under the name Bina Quat P 100 bythe company Ciba-Geigy;

copolymers of acrylamide and of methacryloyloxyethyltrimethylammoniummethosulfate, such as that sold under the name Reten by the companyHercules;

optionally quaternized vinylpyrrolidone/dialkyl-aminoalkyl(meth)acrylate copolymers, which are disclosed, for example, in FrenchPatents 2,077,143 and 2,393,573, the disclosures of which relating tocationic polymers are incorporated herein by reference, and sold, forexample, under the name “Gafquat” by the company ISP, such as, forexample, “Gafquat 734” or “Gafquat 755”, or else the products named“Copolymer 845, 958 and 937”;

dimethylaminoethyl methacrylate/vinylcaprolactam/vinylpyrrolidoneterpolymers, such as the product sold under the name Gaffix VC 713 bythe company ISP, and

the quaternized vinylpyrrolidone/dimethylamino-propylmethacrylamidecopolymer, such as the product sold under the name “Gafquat HS 100” bythe company ISP;

(2) the quaternized polysaccharides, disclosed more particularly in U.S.Pat. Nos. 3,589,578 and 4,031,307, the disclosures of which relating toquaternized polysaccharides polymers are incorporated herein byreference, such as guar gums comprising cationic trialkylammoniumcationic groups.

Such products are sold in particular under the trade names Jaguar C13 S,Jaguar C 15, and Jaguar C 17 by the company Meyhall.

(3) quaternized copolymers of vinylpyrrolidone and of vinylimidazole,such as the products sold by BASF under the name Luviquat TFC.

(4) chitosans or their salts. The salts, which can be used, are inparticular chitosan acetate, lactate, glutamate, gluconate, orpyrrolidone-carboxylate.

Mention may be made, among these compounds, of the chitosan having adegree of deacetylation of 90.5% by weight sold under the name KytanCrude Standard by the company Aber Technologies and the chitosanpyrrolidone-carboxylate sold under the name Kytamer PC by the companyAmerchol.

(5) Cationic cellulose derivatives, such as the copolymers of celluloseor the cellulose derivatives grafted with a water-soluble quaternaryammonium monomer and disclosed in particular in U.S. Pat. No. 4,131,576,the disclosure of which relating to cationic cellulose derivatives isincorporated herein by reference. Examples include hydroxyalkylcelluloses, for example hydroxymethyl, hydroxyethyl, and hydroxypropylcelluloses grafted in particular with amethacryloylethyltrimethylammonium,methacrylamidopropyltrimethylammonium, or diallyldimethylammonium salt.

The commercial products corresponding to this definition are moreparticularly the products sold under the name “Celquat L 200” and“Celquat H 100” by the company National Starch.

The anionic fixing polymers, which can be used according to the presentinvention, are polymers comprising groups derived from carboxylic,sulphonic, and/or phosphoric acid and having a weight average molecularweight ranging from about 500 to about 5,000,000.

(1) The carboxyl groups may be contributed by unsaturated mono- ordicarboxylic acid monomers such as those corresponding to the formula:

in which n is an integer ranging from 0 to 10; A₁ denotes a methylenegroup and when n is greater than 1, each A₁ is independently representedby —LCH₂—, where L is a valency bond or a heteroatom, such as oxygen orsulphur atom; R₇ is a radical chosen from hydrogen, phenyl groups, andbenzyl groups; R₈ is a radical chosen from hydrogen, lower alkyl groups,and carboxyl groups; and R₉ is a radical chosen from hydrogen, loweralkyl groups, —CH₂—COOH groups, phenyl groups, and a benzyl groups.

In the above-mentioned formula, a lower alkyl radical denotes a grouphaving 1 to 4 carbon atoms, such as methyl and ethyl.

The anionic fixing polymers comprising carboxyl groups according to theinvention may be chosen from:

A) Homopolymers and copolymers of (meth)acrylic or (emth)acrylic saltsand in particular the products sold under the names Versicol E or K bythe company Allied Colloid and Ultrahold by the company BASF, thecopolymers of acrylic acid and of acrylamide sold in the form of theirsodium salt under the names Reten 421, 423, or 425 by the companyHercules, and the sodium salts of polyhydroxycarboxylic acids.

B) Copolymers of (meth)acrylic acid with a monoethylenic monomer, suchas ethylene, styrene, vinyl esters, and (meth)acrylic acid esters,optionally grafted onto a polyalkylene glycol, such as polyethyleneglycol, and optionally crosslinked. Such polymers are disclosed inparticular in French Patent 1,222,944 and German Application 2,330,956,the disclosures of which relating to such copolymers are incorporatedherein by reference. The copolymers of this type comprising, in theirchain, an optionally N-alkylated and/or hydroxyalkylated acrylamideunit, such as disclosed in particular in Luxembourg Patent Applications75370 and 75371, the disclosures of which relating to such copolymersare incorporated herein by reference, or sold under the name Quadramerby the company American Cyanamid. Mention may also be made of copolymersof acrylic acid and of C₁-C₄ alkyl methacrylate and terpolymers ofvinylpyrrolidone, of acrylic acid, and of C₁-C₂₀ alkyl methacrylate forexample lauryl methacrylate, such as that sold by the company ISP underthe name Acrylidone L M, and methacrylic acid/ethyl acrylate/tert-butylacrylate terpolymers, such as the product sold under the name Luvimer100 P by the company BASF.

C) copolymers derived from crotonic acid, such as those comprising, intheir chain, vinyl acetate or propionate units and optionally othermonomers, such as (meth)allyl esters, vinyl ether or vinyl ester of alinear or branched saturated carboxylic acid comprising a longhydrocarbon chain, such as those comprising at least 5 carbon atoms, itoptionally being possible for these polymers to be grafted andcrosslinked, or alternatively a vinyl, allyl, or methallyl ester of anα- or β-cyclic carboxylic acid. Such polymers are disclosed, inter alia,in French Patents 1,222,944, 1,580,545, 2,265,782, 2,265,781, 1,564,110,and 2,439,798, the disclosures of which relating to copolymers ofcrotonic acid are incorporated herein by reference. Commercial productscoming within this class are the Resins 28-29-30, 26-13-14, and 28-13-10sold by the company National Starch.

D) copolymers derived from C₄-C₈ monounsaturated carboxylic acids oranhydrides chosen from:

copolymers comprising units derived from (i) one or more maleic,fumaric, or itaconic acids or anhydrides and (ii) at least one monomerchosen from vinyl esters, vinyl ethers, vinyl halides, phenylvinylderivatives, acrylic acids, and acrylic acid esters, the anhydridefunctional groups of these copolymers optionally being monoesterified ormonoamidated. Such polymers are disclosed in particular in U.S. Pat.Nos. 2,047,398, 2,723,248, and 2,102,112 and GB 839,805, the disclosuresof which relating to such copolymers are incorporated herein byreference, and in particular those sold under the names Gantrez AN or ESby the company ISP.

copolymers comprising units derived from (i) one or more maleic,citraconic, or itaconic anhydrides and (ii) one or more monomers chosenfrom (meth)allyl esters, optionally comprising one or more(meth)acrylamide, α-olefin, (meth)acrylic ester, (meth)acrylic acid, orvinylpyrrolidone groups in their chain. The anhydride functional groupsof these copolymers optionally being monoesterified or monoamidated.

These polymers are, for example, disclosed in French Patents 2,350,384and 2,357,241 the disclosures of which relating to such copolymers areincorporated herein by reference.

E) polyacrylamides comprising carboxylate groups.

(2) The anionic fixing polymers comprising sulfonic groups may be chosenfrom polymers comprising units, such as those derived fromvinylsulphonic, styrenesulphonic, naphthalenesulphonic, andacrylamidoalkylsulphonic acids and their derivatives. These polymers maybe chosen from:

salts of polyvinylsulphonic acid having a weight average molecularweight that ranges from about 1000 to about 100,000, as well as thecopolymers with an unsaturated comonomer, such as acrylic andmethacrylic acids, their esters, acrylamides, their derivatives, vinylethers, and vinylpyrrolidone;

salts of polystyrenesulphonic acid, the sodium salts having a weightaverage molecular weight ranging from about 100,000 to about 500,000,which are sold respectively under the names Flexan 500 and Flexan 130 byNational Starch. These compounds are disclosed in Patent FR 2,198,719,the disclosure of which relating to salt of polystyrenesulphonic acid isincorporated herein by reference;

salts of polyacrylamidesulphonic acids, including those mentioned inU.S. Pat. No. 4,128,631, the disclosure of which relating to salt ofpolyacrylamidesulphonic acid is incorporated herein by reference, andmore particularly the polyacrylamidoethylpropanesulphonic acid soldunder the name Cosmedia Polymer HSP 1180 by Henkel.

In one embodiment, the anionic fixing polymers are chosen from acrylicacid copolymers, such as the acrylic acid/ethylacrylate/N-tert-butylacrylamide terpolymer sold under the name UltraholdStrong by the company BASF; copolymers derived from crotonic acid, suchas the vinyl acetate/vinyl tert-butyl-benzoate/crotonic acid terpolymersand the crotonic acid/vinyl acetate/vinyl neododecanoate terpolymerssold under the name Resin 28-29-30 by the company National Starch;polymers derived from maleic, fumaric, or itaconic acids or anhydrideswith vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives,or acrylic acid and its esters, such as the monoesterified methyl vinylether/maleic anhydride copolymer sold under the name Gantrez ES 425 bythe company ISP; copolymers of methacrylic acid and of methylmethacrylate sold under the name Eudragit L by the company Rohm Pharma;the copolymer of methacrylic acid and of ethyl acrylate sold under thename Luvimer MAEX or MAE by the company BASF; the vinyl acetate/crotonicacid copolymer sold under the name Luviset CA 66 by the company BASF;and the vinyl acetate/crotonic acid copolymer grafted by polyethyleneglycol sold under the name Aristoflex A by the company BASF.

In another embodiment, the anionic fixing polymers are chosen from themonoesterified methyl vinyl ether/maleic anhydride copolymer sold underthe name Gantrez ES 425 by the company ISP; the acrylic acid/ethylacrylate/N-tert-butylacrylamide terpolymer sold under the name UltraholdStrong by the company BASF; the copolymers of methacrylic acid and ofmethyl methacrylate sold under the name Eudragit L by the company RohmPharma; the vinyl acetate/vinyl tert-butylbenzoate/crotonic acidterpolymers and the crotonic acid/vinyl acetate/vinyl neododecanoateterpolymers sold under the name Resin 28-29-30 by the company NationalStarch; the copolymer of methacrylic acid and of ethyl acrylate soldunder the name Luvimer MAEX or MAE by the company BASF; and thevinyl-pyrrolidone/acrylic acid/lauryl methacrylate terpolymer sold underthe name Acrylidone LM by the company ISP.

The amphoteric fixing polymers, which can be used in accordance with theinvention, may be chosen from polymers comprising X and Y units,distributed randomly in the polymer chain, where the X unit is chosenfrom units derived from at least one monomer comprising at least onebasic function, in particular a basic nitrogen atom, and where the Yunit is chosen from units derived from at least one acidic monomercomprising at least one group chosen from carboxyl groups and sulphogroups, or else where each X and Y unit is independently chosen fromgroups derived from zwitterionic carboxybetaine and sulphobetainemonomers. In another embodiment, the amphoteric fixing polymers, whichcan be used in accordance with the invention, may be chosen frompolymers comprising X and Y units, each X and Y unit is independentlychosen from at least one cationic polymer chain comprising at least onegroup chosen from primary amine groups, secondary amine groups, tertiaryamine groups, and quaternary amine groups, in which at least one of theamine groups comprises a carboxyl or sulpho group linked by way of ahydrocarbon radical, or else the X and Y units, which may be differentor identical, form part of a chain of at least one polymer comprising anα,β-dicarboxy ethylene unit, wherein at least one of the carboxyl groupshas been reacted with a polyamine comprising at least one group chosenfrom primary and secondary amine groups.

In one embodiment, the amphoteric fixing polymers corresponding to thedefinition given above are chosen from the following polymers:

(1) polymers resulting from the copolymerization of a monomer derivedfrom a vinyl compound carrying a carboxyl group, such as (meth)acrylicacids, maleic acids, and α-chloracrylic acids, and of a basic monomerderived from a substituted vinyl compound comprising at least one basicatom, such as dialkylaminoalkyl (meth)acrylate and dialkylaminoalkyl(meth)acrylamide. Such compounds are disclosed in U.S. Pat. No.3,836,537, the disclosure of which relating to amphoteric polymers isincorporated herein by reference.

(2) polymers comprising units derived from:

a) at least one monomer chosen from (meth)acrylamides substituted on thenitrogen with an alkyl radical,

b) at least one acidic comonomer comprising at least one reactivecarboxylic group, and

c) at least one basic comonomer, such as esters comprising primary,secondary, tertiary, and quaternary amine substituents of (meth)acrylicacids and the product of quaternization of dimethylaminoethylmethacrylate with dimethyl or diethyl sulfate.

The at least one (a) N-substituted (meth)acrylamides are moreparticularly chosen from N-substituted (meth)acrylamides, wherein thealkyl radicals comprise from 2 to 12 carbon atoms, such asN-ethylacrylamide, N-tert-butylacrylamide, N-tert-octylacrylamide,N-octylacrylamide, N-decylacrylamide, N-dodecylacrylamide, and thecorresponding methacrylamides.

The at least one (b) acidic comonomer is more particularly chosen from(meth)acrylic acids, crotonic acids, itaconic acids, maleic acids,fumaric acids, C₁-C₄ alkyl monoesters of maleic acid, C₁-C₄ alkylmonoesters of fumaric acid, C₁-C₄ alkyl monoesters of maleic anhydride,and C₁-C₄ alkyl monoesters of fumaric anhydride.

The at least one (c) basic comonomers is more particularly chosen fromaminoethyl, butylaminoethyl, N,N′-dimethylaminoethyl, andN-tert-butylaminoethyl methacrylates.

In one embodiment, the amphoteric fixing polymer is chosen from thecopolymers for which the CTFA name (4th Ed., 1991) is octylacrylamide/acrylates/butylaminoethyl methacrylate copolymer, such as the productssold under the name Amphomer or Lovocryl 47 by the company NationalStarch.

(3) crosslinked and alkylated polyamino amides partially or totallyderived from polyamino amides of general formula:

CO—R₁₀—CO—Z  (III)

in which R₁₀ represents a divalent radical derived either from asaturated dicarboxylic acid, from an aliphatic mono- or dicarboxylicacid comprising an ethylenic double bond, from an ester of a loweralkanol having 1 to 6 carbon atom of these acids, or from a radicalderived from the addition of any one of the said acids with a bisprimaryor bissecondary amine; and Z denotes a radical of a bisprimary, mono- orbissecondary polyalkylenepolyamine and, for example, represents:

a) in the proportions of from about 60 mol % to 100 mol %, the radical:

—NH(CH₂)_(x)—NH_(p)  (IV)

 where x=2 and p=2 or 3, or else x=3 and p=2 and where this radicalderives from diethylenetriamine, triethylenetetraamine, ordipropylenetriamine;

b) in the proportions of from 0 mol % to about 40 mol %, the aboveradical (IV), in which x=2 and p=1 and which derives fromethylenediamine, or the radical derived from piperazine:

c) in the proportions of from 0 mol % to about 20 mol %, the—NH—(CH₂)₆—NH— radical derived from hexamethylenediamine, thesepolyamino amines being crosslinked by addition of a difunctionalcrosslinking agent chosen from epihalohydrines, diepoxides, dianhydridesand bis-unsaturated derivatives, using from about 0.025 mol to about0.35 mol of crosslinking agent per amine group of the polyamino amideand alkylated by the action of acrylic acid, chloroacetic acid or analkane sultone, or salts thereof.

In one embodiment, the saturated carboxylic acids are chosen from acidshaving 6 to 10 carbon atoms, such as adipic acid, 2,2,4-trimethyladipicacid, 2,4,4-trimethyladipic acid, terephthalic acid, and acidscomprising an ethylenic double bond such as, for example, acrylic acid,methacrylic acid and itaconic acid.

In one embodiment, the alkane sultones used in the alkylation are chosenfrom propane sultone and butane sultone and the salts of the alkylatingagents are chosen from sodium and potassium salts.

(4) polymers comprising zwitterionic units of formula:

in which R₁₁ is chosen from polymerizable unsaturated groups such as an(meth)acrylate and (meth)acrylamide groups; y and z are independentlychosen from integers ranging from 1 to 3; R₁₂ and R₁₃ are independentlychosen from hydrogen, methyl groups, ethyl groups, and propyl groups;R₁₄ and R₁₅ are independently chosen from hydrogen and alkyl radicals,wherein the sum of the carbon atoms in R₁₄ and R₁₅ is less than or equalto 10.

The polymers comprising such units may further comprise units derivedfrom non-zwitterionic monomers, such as dimethylaminoethyl(meth)acrylate, diethylaminoethyl (meth)acrylate, alkyl (meth)acrylates,(meth)acrylamides, and vinyl acetates.

Mention may be made, by way of example, of the methylmethacrylate/methyl dimethylcarboxymethylammonioethyl methacrylatecopolymer, such as the product sold under the name Diaformer Z301 by thecompany Sandoz.

(5) polymers derived from chitosan comprising monomer unitscorresponding to the following formulae:

the unit D being present in proportions ranging from 0% to about 30%,the unit E in proportions ranging from about 5% to about 50% and theunit F in proportions ranging from about 30% to about 90%, it beingunderstood that, in this unit F, R₁₆ represents a radical of formula:

in which, if q=0, R₁₇, R₁₈, and R₁₉, which are identical or different,are chosen from hydrogen, methyl groups, hydroxyl groups, acetoxygroups, amino residues, monoalkylamine residues, and dialkylamineresidues, optionally interrupted by one or more nitrogen atoms and/oroptionally substituted by one or more amine, hydroxyl, carboxy,alkylthio, or sulpho groups, and alkylthio residues in which the alkylgroup carries an amino residue, at least one of the R₁₇, R₁₈, and R₁₉radicals being, in this case, hydrogen; or, if q=1, R₁₇, R₁₈, and R₁₉each represent hydrogen, and the salts formed by these compounds withbases or acids.

(6) Polymers derived from the N-carboxyalkylation of chitosan, such asthe N-(carboxymethyl)chitosan or the N-(carboxybutyl)chitosan sold underthe name “Evalsan” by the company Jan Dekker.

(7) Polymers corresponding to the general formula (VI), for exampledisclosed in French Patent 1,400,366, the disclosure of which relatingto amphoteric polymers is incorporated herein by reference:

in which R₂₀ is a radical chosen from hydrogen, CH₃O, CH₃CH₂O, andphenyl radicals; R₂₁ is chosen from hydrogen and lower alkyl radicalssuch as methyl or ethyl; R₂₂ is chosen from hydrogen and lower alkylradicals such as methyl or ethyl; and R₂₃ is chosen from lower alkylradicals such as methyl or ethyl and radicals corresponding to theformula: —R₂₄—N(R₂₂)₂, where R₂₄ represents a —CH₂—CH₂—, —CH₂—CH₂—CH₂—,or —CH₂—CH(CH₃)— group and R₂₂ is the same as above, and the higherhomologues of these radicals comprising up to 6 carbon atoms.

(8) Amphoteric fixing polymers of the —D—X—D—X— type chosen from:

a) polymers obtained by reaction of chloracetic acid or sodiumchloracetate with compounds comprising at least one unit of formula:

—D—X—D—X—D—  (VI)

where D denotes a radical

 and X denotes the symbol E or E′. E and E′, which are identical ordifferent, denote a divalent radical chosen from straight- andbranched-chain alkylene radicals comprising up to 7 carbon atoms in themain chain, which is unsubstituted or substituted by hydroxyl groups andwhich can additionally comprise oxygen, nitrogen, or sulphur atoms or 1to 3 aromatic and/or heterocyclic rings; the oxygen, nitrogen, andsulphur atoms being present in the form of ether, thioether, sulphoxide,sulphone, sulphonium, alkylamine or alkenylamine groups, benzylamine,amine oxide, quaternary ammonium, amide, imide, alcohol, ester, and/orurethane groups.

b) Polymers of formula:

—D—X—D—X—  (VII′)

 in which D denotes a radical

 and X denotes the symbol E or E′ and E′ at least once, where E has themeaning indicated above and E′ is a divalent radical chosen fromstraight- and branched-chain alkylene radicals having up to 7 carbonatoms in the main chain, which is substituted or unsubstituted by one ormore hydroxyl radicals and which comprises one or more nitrogen atoms,the nitrogen atom being substituted by an alkyl chain optionallyinterrupted by an oxygen atom and necessarily comprising one or morecarboxyl functional groups or one or more hydroxyl functional groups andwherein the polymer of formula VII′ is betainized by reaction withchloracetic acid or sodium chloracetate.

(9) (C₁-C₅)alkyl vinyl ether/maleic anhydride copolymers, which arepartially modified by semiamidation with an N,N-dialkylaminoalkylamine,such as N,N-dimethylaminopropylamine, or by semiesterification with anN,N-dialkanolamine. These copolymers can also comprise other vinylcomonomers, such as vinylcaprolactam.

In one embodiment, the amphoteric fixing polymers according to theinvention are chosen from family (3), such as the copolymers with theCTFA name (4^(th) Ed. 1991) of octylacrylamide/acrylates/butylaminoethylmethacrylate copolymer, such as the products sold under the namesAmphomer, Amhomer LV 71, or Lovocryl 47 by the company National Starch,and family (4), such as the copolymer of methyl methacrylate/dimethylcarboxymethylammonio methyl ethylmethacrylate, sold, for example, underthe name Diaformer Z301 by the company Sandoz.

The nonionic fixing polymers, which can be used according to the presentinvention, are chosen, for example, from:

vinylpyrrolidone homopolymers;

copolymers of vinylpyrrolidone and of vinyl acetate;

polyalkyloxazolines, such as the polyethyloxazolines sold by the companyDow Chemical under the names PEOX 50 000, PEOX 200 000 and PEOX 500 000;

vinyl acetate homopolymers, such as the product sold under the nameAppretan EM by the company Hoechst or the product sold under the nameRhodopas A 012 by the company Rhône-Poulenc;

copolymers of vinyl acetate and of acrylic ester, such as the productsold under the name Rhodopas AD 310 by Rhône-Poulenc;

copolymers of vinyl acetate and of ethylene, such as the product soldunder the name Appretan TV by the company Hoechst;

copolymers of vinyl acetate and of maleic ester, for example of dibutylmaleate, such as the product sold under the name Appretan MB Extra bythe company Hoechst;

copolymers of polyethylene and of maleic anhydride;

alkyl acrylate homopolymers and alkyl methacrylate homopolymers, such asthe product sold under the name Micropearl RQ 750 by the companyMatsumoto or the product sold under the name Luhydran A 848 S by thecompany BASF;

acrylic ester copolymers such as, for example, copolymers of alkyl(meth)acrylates, such as the products sold by the company Rohm & Haasunder the names Primal AC-261 K and Eudragit NE 30 D, by the companyBASF under the names Acronal 601, Luhydran LR 8833 or 8845, and by thecompany Hoechst under the names Appretan N 9213 or N 9212;

copolymers of acrylonitrile and of a nonionic monomer chosen, forexample, from butadiene and alkyl (meth)acrylates; mention may be madeof the products sold under the names Nipol LX 531 B by the companyNippon Zeon or those sold under the name CJ 0601 B by the company Rohm &Haas;

polyurethanes, such as the products sold under the names Acrysol RM 1020or Acrysol RM 2020 by the company Rohm & Haas, and the products UraflexXP 401 UZ and Uraflex XP 402 UZ by the company DSM Resins;

copolymers of alkyl acrylate and of urethane, such as the product8538-33 by the company National Starch;

polyamides, such as the product Estapor LO 11 sold by the companyRhône-Poulenc.

nonionic guar gums that are chemically modified or unmodified.

The unmodified nonionic guar gums are, for example, the products soldunder the name Vidogum GH 175 by the company Unipectine and under thename Jaguar C by the company Meyhall.

The modified nonionic guar gums, which may be used according to theinvention, are, for example, modified with C₁-C₆ hydroxyalkyl groups.Examples, which may be mentioned, are hydroxymethyl, hydroxyethyl,hydroxypropyl and hydroxybutyl groups.

These guar gums are well known in the prior art and may be prepared, forexample, by reacting corresponding alkene oxides such as, for example,propylene oxides with guar gum so as to obtain a guar gum modified withhydroxypropyl groups.

Such nonionic guar gums, optionally modified with hydroxyalkyl groups,are sold, for example, under the trade names Jaguar HP8, Jaguar HP60,Jaguar HP120, Jaguar DC 293 and Jaguar HP 105 by the company Meyhall andunder the name Galactosol 4H4FD2 by the company Aqualon.

The alkyl radicals in the nonionic polymers comprise from 1 to 6 carbonatoms, except where otherwise mentioned.

According to the invention, it is also possible to use fixing polymersof grafted silicone type comprising a polysiloxane portion and a portioncomposed of a non-silicone organic chain, one of the two portionsconstituting the main chain of the polymer and the other being graftedonto the said main chain. These polymers are disclosed, for example, inEP-A-0,412,704, EP-A-0,412,707, EP-A-0,640,105, WO 95/00578,EP-A-0,582,152, and WO 93/23009 and U.S. Pat. Nos. 4,693,935, 4,728,571,and 4,972,037, the disclosures of which relating to grafted siliconetype polymers are incorporated herein by reference. These polymers are,for example, anionic or nonionic.

Such polymers are, for example, copolymers which can be obtained byradical polymerization from the monomer mixture comprising:

a) about 50% to about 90% by weight of tert-butyl acrylate;

b) 0% to about 40% by weight of acrylic acid;

c) about 5% to about 40% by weight of silicone macromer of formula:

 where v is a number ranging from 5 to 700; the percentages by weightbeing calculated with respect to the total weight of the monomers.

Other examples of grafted silicone polymers are, in particular,polydimethylsiloxanes (PDMSs) onto which are grafted, via athiopropylene-type connecting chain, mixed polymer units of thepoly(meth)acrylic acid type and of the poly(alkyl (meth)acrylate) typeand polydimethylsiloxanes (PDMSs) onto which are grafted, via athiopropylene-type connecting chain, polymer units of the poly(isobutyl(meth)acrylate) type.

It is also possible to use, as fixing polymers, functionalized ornon-functionalized and silicone-comprising or non-silicone-comprisingpolyurethanes.

The polyurethanes particularly targeted by the present invention arethose disclosed in Patents EP 0,751,162, EP 0,637,600, FR 2,743,297, EP0,648,485, EP 0,656,021, WO 94/03510, and EP 0,619,111, the disclosureof which relating to poylurethanes are incorporated herein by reference.

In a further embodiment, the fixing polymers may be used in solubilizedform or may be in the form of dispersions of solid particles (latex orpseudo-latex).

The compositions according to the invention can be provided in any formknown from the prior art, which is appropriate for their application tothe hair, including in the form of a vaporizable composition such assprays and aerosols, mousse, gel, stick, mud, or lotion.

The composition may be in any of the conventional forms of cosmeticcomposition including, but not limited to, shampoos, hair rinses,permanent waving compositions, waving compositions, hair dyecompositions, hair straightening compositions, hair fixing products,hair styling gel products, products to use before or after a hair dyetreatment, products to use before or after a permanent waving treatment,hair straightening compositions, products to use before or after a hairstraightening treatment, and fixing foams.

The composition according to the invention may be vaporizable, forexample by a pump, or may be a pressurized aerosol composition. It maybe vaporizable by a dispensing valve controlled by a dispensing head,which in turn comprises a nozzle, which vaporizes the aerosolcomposition. A vaporizable composition according to the inventioncomprises an appropriate solvent. Advantageously, the appropriatesolvent comprises at least one solvent chosen from water and loweralcohols. In accordance with the invention, the term lower alcohol meansa C₁ to C₄ aliphatic alcohol, such as ethanol.

When the vaporizable composition according to the invention is anaerosol composition, it additionally comprises an appropriate amount ofpropellant. The propellant comprises compressed or liquefied gases,which are normally employed for the preparation of aerosol compositions.Suitable gasses include compressed air, carbon dioxide, nitrogen, andgases, which may be soluble in the composition, such as dimethyl ether,fluorinated or non-fluorinated hydrocarbons, and mixtures thereof.

The present invention additionally provides an aerosol device comprisinga vessel comprising an aerosol composition, which comprises a liquidphase (or juice) comprising at least one hair styling material, asdescribed above, in an appropriate medium and a propellant, and adispenser, such as a dispensing valve, for dispensing said aerosolcomposition from the vessel.

The present invention additionally provides a method of treatingkeratinous fibers, especially hair, in which the composition accordingto the invention, as described above, is applied to the hair before,during, or after the shaping of the hairstyle.

The compositions according to the invention can be rinsed off or notrinsed off the hair.

The present invention additionally provides the use of a composition asdescribed above in, or for the preparation of, a cosmetic reshapablehair styling formulation.

The determination of whether a composition with a (meth)acryliccopolymer according to the invention can provide a reshapable effect canbe determined by an in vivo test.

Where the composition is in the form of a lotion, for example, the invivo test proceeds as follows. The hair of the model is washed and thendivided into two symmetrical portions, the right and the left sides. Thecomposition is applied to one side of the head of the model, while areference composition is applied to the other side of the head. Thereference composition may, for example, be chosen from water, anexisting commercial product, or another composition under study. Thehairdresser dries and styles both sides of the head. The two sides ofthe head are separately evaluated for the styling effect, the cosmeticproperties, and the reshapable effect. For example, once dried, the hairis brushed in different directions to remove the original styling. Thehair is then brushed to restore the original styling. The process ofremoving the styling, restoring the styling, and evaluating the successof restoring the styling is repeated at least one more time to determinewhether the composition is a reshapable hair styling composition. Areshapable hair styling composition permits (1) the original hairstyling to be restored after brushing and (2) the creation of a new hairstyling after brushing, which may also be restored after brushing. Ifthe composition to be evaluated is in another form, such as a shampoo orconditioner, the in vivo test can be appropriately modified by oneskilled in the art.

It is understood that the person skilled in the art would recognize thatnot all formulations would provide reshapable effect for all hair typesduring in vivo testing and will know how to formulate and evaluatereshapable hair styling composition in view of the various hairparameters, such as length (short versus long), diameter (thin versusthick), structure (curly versus straight), condition (oily, dry, ornormal); and whether the hair is colored, bleached, permed, orstraightened. Thus, in vivo testing may require testing on 10-20different individuals.

Other than in the operating examples, or where otherwise indicated, allnumbers expressing quantities of ingredients, reaction conditions, andso forth used in the specification and claims are to be understood asbeing modified in all instances by the term “about.” Accordingly, unlessindicated to the contrary, the numerical parameters set forth in thefollowing specification and attached claims are approximations that mayvary depending upon the desired properties sought to be obtained by thepresent invention. At the very least, and not as an attempt to limit theapplication of the doctrine of equivalents to the scope of the claims,each numerical parameter should be construed in light of the number ofsignificant digits and ordinary rounding approaches.

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the invention are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspossible. Any numerical value, however, inherently contains certainerrors necessarily resulting from the standard deviation found in theirrespective testing measurements.

The invention may be understood more clearly with the aid of thenon-limiting examples that follow, and which constitute an advantageousembodiment of the compositions in accordance with the invention.

EXAMPLES

Hair compositions according to the invention, as well as comparativecompositions, were produced with different (meth)acrylic copolymers.Percentages given are by weight, unless otherwise specified.

1) Preparation of the (Meth)acrylic Copolymers Example 1 TetrapolymerMade by Semi-continuous Emulsion Polymerization

A solution of 1.0 grams carbon tetrabromide was prepared in a mixture of275 grams 2-ethylhexyl acrylate (2-EHA), 200 grams isobornyl acrylate(IBOA), 12.5 grams methacrylic acid (MMA), and 12.5 grams acrylic acid(AA) yielding 500 grams of a monomer solution containing 55/4012.5/2.5parts 2-EHA/IBOA/MAA/AA. Of the total monomer solution, 50 grams wascharged into a two liter split resin flask along with 390 grams ofdeionized water and 0.5 gram of sodium dodecyl benzene sulfonate. Thehead was placed on the flask and a thermocouple, nitrogen inlet, andmechanical stirrer attached. The contents were heated with infraredlamps to about 60° C. while stirring at 350 rpm. A solution of 1.25grams potassium persulfate in 20 grams deionized water was charged, theflask sealed, and a vacuum pulled on the flask four times, breaking iteach time with nitrogen. The flask was held at 60° C. for 20 minutes,then heated to 80° C. over 10 minutes to yield a seed polymer. Apre-emulsion of the remaining 450 grams of the monomer solution wasprepared by charging a solution of 4.5 grams of sodium dodecyl benzenesulfonate in 201 grams of deionized water to it and stirring undernitrogen. This pre-emulsion was added dropwise to the two liter splitresin flask containing the seed polymer at a rate of 6 grams per minute.The addition took almost 2 hours. After the addition, the stirring ratewas reduced to 200 rpm and the reaction held at 80° C. for two hours,then the resulting latex was filtered through doubled over cheeseclothinto a jar. Low levels of coagulum were noted around the thermocoupleand stirring paddle.

Example 2 Tetrapolymer May be Made by Match Emulsion Polymerization

Into a one liter Mortonized split resin flask may be charged 100 gramsof monomers (45 grams 2-EHA, 35 grams IBOA, 10 grams MM, and 10 gramsAA), 80 milligrams of carbon tetrabromide, 124.7 grams of deionizedwater, 200 milligrams of potassium persulfate, 64 milligrams of sodiummetabisulfite, 1 gram of sodium dodecyl benzene sulfonate, and 2.5 gramsof Mazon SAM 211 alkylene polyalkoxy ammonium sulfate copolymerizablesurfactant (available from PPG Industries, Pittsburgh, Pa.). The head isplaced on the flask and a thermocouple, nitrogen inlet, and mechanicalstirrer are attached. The headspace is swept with nitrogen at 1 literper minute while heating the contents with infrared lamps to about 30°C. and stirring at 250 rpm. About 1 gram of a solution of 28 milligramsferrous sulfate heptahydrate in 50 grams deionized water is charged, theflask sealed, and a vacuum pulled on the flask three times, breaking iteach time with nitrogen. After 15 or 20 minutes an exotherm is notedwhich peaks 20 to 25 minutes later at 55° C. to 65° C. Reactortemperature is increased to about 75° C. and held for one hour, then theresulting latex is filtered through doubled over cheesecloth into a jar.

Example 3 Tetrapolymer May be Made by Solution Polymerization andInversion in Water

Into a 120 milliliter glass bottle may be charged with 24 grams ofmonomers (8.4 grams 2-EHA, 13.2 grams cyclohexyl methacrylate (CHXMA),1.2 grams MAA, and 1.2 grams AA), 120 milligrams of carbon tetrabromide,36 grams of methylethyl ketone, and 72 milligrams ofazobis(isobutyronitrile). The contents of the bottle are swept withnitrogen at about 1 liter per minute for two minutes, then the bottle iscapped and tumbled in a water bath for 24 hours at about 55° C. to yielda moderate viscosity solution. 15 grams (containing 6 grams of polymeror 8.3 milliequivalents of carboxylic acid) of the resulting solution ischarged into a 250 milliliter round bottom flask containing a solutionof 0.67 grams (7.5 milliequivalents, 90% neutralization) of2-amino-2-methyl-1-propanol in 14 grams of deionized water with moderateagitation. The solvent is removed from the resulting dispersion by arotary evaporator set at about 63° C. at a reduced pressure of 40kilopascals to yield a milky white dispersion.

Example 4 Pentapolymer May be Made by Suspension Polymerization

In a one liter Mortonized split resin flask may be charged 240 gram of amonomer mixture (120 grams 2-EHA, 54 grams IBOA, 54 grams (CHXMA), 6grams MAA, and 6 grams AA). Added to the flask is 6.9 grams Ludox™ 50(50% by wt colloidal silica in water, available from Aldrich, Milwaukee,Wis.), 360 grams deionized water, 0.42 grams adipic acid/diethanol aminecondensate (a 50% solids used as a promoter, is prepared according tothe procedure disclosed in U.S. Pat. No. 5,238,736), and 0.08 gramspotassium dichromate. The head is placed on the flask and athermocouple, nitrogen inlet, and mechanical stirrer are attached. Theentire content inside the flask is mixed. The pH is measured andadjusted by adding ammonium hydroxide to a pH between 4 and 5. Themixture is then transferred to a Waring™ blender and exposed to highshear (about 22,000 rpm) for six minutes total, using shear for abouttwo minutes at a time to avoid overheating the mixture.

The mixture is then returned to the Mortonized flask and 0.36 grams ofVazo™ 64 (azo-bis(isobutyronitrile) initiator, available from E.I. duPont de Nemours & Co., Wilmington, Del.) is added. A nitrogen purge isstarted and the mixture is agitated gently for several minutes to letthe initiator dissolve. The agitation speed is adjusted to about 300 rpmand the temperature is set at about 60° C. The reaction is startedwithin minutes and is allowed to exotherm. After exotherming, thetemperature is maintained at about 60° C. for about four hours.

Example 5

A 50/50 mixture of the emulsion from Example 1 and a dispersioncomprising AQ 1350 by the Eastman Chemical Co. as disclosed in WO98/38969 may be made.

Example 6

A 25/75 mixture of the emulsion from Example 1 and the emulsion fromExample 2 may be made.

2) Preparation of Comparative Terpolymers Comparative Examples A and BTerpolymers Made by Batch Emulsion Polymerization

Into a one liter Mortonized split resin flask was charged 100 grams ofmonomers (detailed in Table I below), 80 milligrams of carbontetrabromide, 124.7 grams of deionized water, 200 milligrams ofpotassium persulfate, 64 milligrams of sodium metabisulfite, 1 gram ofsodium dodecyl benzene sulfonate, and 2.5 grams of Mazon SAM 211alkylene polyalkoxy ammonium sulfate copolymerizable surfactant(available from PPG Industries, Pittsburgh, Pa.). The head was placed onthe flask and a thermocouple, nitrogen inlet, and mechanical stirrerattached. The headspace was swept with nitrogen at 1 liter per minutewhile heating the contents with infrared lamps to about 30° C. andstirring at 250 rpm. About 1 gram of a solution of 28 milligrams ferroussulfate heptahydrate in 50 grams deionized water was charged, the flasksealed, and a vacuum pulled on the flask three times, breaking it eachtime with nitrogen. After 15 or 20 minutes an exotherm is noted whichpeaks 20 to 25 minutes later at 55° C. to 65° C. Reactor temperature isincreased to about 75° C. and held for one hour, then the resultinglatex was filtered through doubled over cheesecloth into a jar. In allcases moderate levels of coagulum were noted around the thermocouple andstirring paddle.

TABLE I Monomer Charges Used for Batch Emulsion Polymerization Example g2-EHA g IBOA g AA g MAA A 60 35 0 5 B 50 45 5 0 2-EHA = 2-ethylhexylacrylate IBOA = isobornyl acrylate AA = acrylic acid MAA = methacrylicacid

3) Preparation of the Hair Styling Compositions

One comparative hair styling composition not in accordance with theinvention and one hair styling composition in accordance with theinvention were prepared using the components and amounts in weightpercent listed hereafter. The testing was conducted on several modelswith one part of the head receiving a reference composition and theother side of the head receiving the tested composition. Thecompositions were applied to wet hair after shampooing. The hair wasthen dried, brushed, and evaluated.

Reference 1: AQ 1350 4% active material Water qsp 100% Reference 2Comparative Example A 2% active material Comparative Example B 2% activematerial Water qsp 100% Formulation A (comparative) Comparative ExampleA 2% active material Comparative Example B 2% active material Water qsp100%

Formulation A imparted very good hairstyling and a very good reshapableeffect with correct cosmetic properties, as compared with Reference 1.

Note: Both Formulation A (comparative) and Reference 2 compriseComparative Examples A and B polymers; however, the polymers were fromseparate batches.

Formulation B: Example 1 4% active material Water qsp 100%

Formulation B imparted very good hairstyling and a very good reshapableeffect with average cosmetic properties, such as untangling, volume, andfeel, as compared with Reference 2. Shine was somewhat better, whilesoftness and body were not optimum, as compared to the reference. Thus,the tetrapolymer (55/40/2.5/2.5 parts 2-EHA/IBOA/MAA/AA) may yield abetter reshapable effect than a comparable blend (60/35/5 parts2-EHA/IBOA/MAA with 50/45/5 parts 2-EHA/IBOA/AA, having a netcomposition of 55/40/2.5/2.5 parts 2-EHA/IBOA/MAA/AA).

What is claimed is:
 1. A reshapable hair styling composition comprisingat least one (meth)acrylic copolymer comprising: (a) from about 20 toabout 80 weight percent of units derived from ethyl hexyl(meth)acrylate, (b) from about 5 to about 65 weight percent of unitsderived from isobornyl (meth)acrylate, (c) from about 1 to about 15weight percent of units derived from acrylic acid, and (d) from about 1to about 15 weight percent of units derived from methacrylic acid,wherein the ratio of ethyl hexyl (meth)acrylate derived units toisobornyl (meth)acrylate derived units ranges from about 0.5:1 to about6:1, wherein said composition provides a reshapable effect.
 2. Thecomposition according to claim 1, wherein the composition furthercomprises a cosmetically acceptable vehicle.
 3. The compositionaccording to claim 1, wherein said at least one (meth)acrylic copolymercomprises (a) about 55 weight percent of units derived from 2-ethylhexyl acrylate, (b) about 40 weight percent of units derived fromisobornyl acrylate, (c) about 2.5 weight percent of units derived fromacrylic acid, and (d) about
 2. 5 weight percent of units derived frommethacrylic acid.
 4. The composition according to claim 1, wherein saidat least one (meth)acrylic copolymer is present in an amount rangingfrom about 0.1 to about 40 weight percent of the total weight percent ofthe composition.
 5. The composition according to claim 4, wherein theamount of said at least one (meth)acrylic copolymer ranges from about0.5 to about 15 weight percent.
 6. The composition according to claim 1,wherein said at least one (meth)acrylic copolymer has a Tg ranging fromabout −100° C. to about 15° C.
 7. The composition according to claim 1,wherein the composition further comprises at least one additionalpolymer.
 8. The composition according to claim 7, wherein said at leastone additional polymer is chosen from anionic, cationic, amphoteric, andnonionic polymers.
 9. The composition according to claim 1, furthercomprising at least one conventional cosmetic constituent chosen frompreservatives, perfumes, active hair care agents, plasticizers, anionic,cationic, amphoteric, and nonionic surfactants, hair conditioningagents, silicone fluids, fatty esters, fatty alcohol, long chainhydrocarbons, emollients, lubricants, penetrants, lanolin compounds,protein hydrolysates, other protein derivatives, dyes, tins, bleaches,reducing agents, pH adjusting agents, sunscreens, and thickening agents.10. A reshapable hair styling composition comprising at least one(meth)acrylic copolymer comprising: (a) from about 20 to about 80 weightpercent of units derived from ethyl hexyl (meth)acrylate, (b) from about5 to about 65 weight percent of units derived from isobornyl(meth)acrylate, (c) from about 1 to about 15 weight percent of unitsderived from acrylic acid, and (d) from about 1 to about 15 weightpercent of units derived from methacrylic acid, wherein the ratio ofethyl hexyl (meth)acrylate derived units to isobornyl (meth)acrylatederived units ranges from about 0.5:1 to about 6:1, wherein saidcomposition provides a reshapable effect and is in the form of a spray,aerosol, mousse, gel, stick, mud, or lotion.
 11. An aerosol devicecomprising a vessel, which comprises: (1) an aerosol composition, whichprovides a reshapable effect and comprises a liquid phase comprising atleast one composition comprising at least one (meth)acrylic copolymercomprising: (a) from about 20 to about 80 weight percent of unitsderived from ethyl hexyl (meth)acrylate, (b) from about 5 to about 65weight percent of units derived from isobornyl (meth)acrylate, (c) fromabout 1 to about 15 weight percent of units derived from acrylic acid,and (d) from about 1 to about 15 weight percent of units derived frommethacrylic acid, wherein the ratio of ethyl hexyl (meth)acrylatederived units to isobornyl (meth)acrylate derived units ranges fromabout 0.5:1 to about 6:1; and wherein said composition provides areshapable effect and a propellant, and (2) a dispenser.
 12. A method ofcosmetically treating hair, comprising applying to the hair before,during, or after shaping of a hairstyle of said hair a compositioncomprising at least one (meth)acrylic copolymer comprising: (a) fromabout 20 to about 80 weight percent of units derived from ethyl hexyl(meth)acrylate, (b) from about 5 to about 65 weight percent of unitsderived from isobornyl (meth)acrylate, (c) from about 1 to about 15weight percent of units derived from acrylic acid, and (d) from about 1to about 15 weight percent of units derived from methacrylic acid,wherein the ratio of ethyl hexyl (meth)acrylate derived units toisobornyl (meth)acrylate derived units ranges from about 0.5:1 to about6:1; and wherein said composition provides a reshapable effect.
 13. Amethod of reshaping hair, comprising: (1) applying to the hair before,during, or after the initial shaping of the hairstyle a compositioncomprising at least one (meth)acrylic copolymer comprising: (a) fromabout 20 to about 80 weight percent of units derived from ethyl hexyl(meth)acrylate, (b) from about 5 to about 65 weight percent of unitsderived from isobornyl (meth)acrylate, (c) from about 1 to about 15weight percent of units derived from acrylic acid, and (d) from about 1to about 15 weight percent of units derived from methacrylic acid,wherein the ratio of ethyl hexyl (meth)acrylate derived units toisobornyl (meth)acrylate derived units ranges from about 0.5:1 to about6:1; and wherein said composition provides a reshapable effect, and (2)thereafter shaping the hairstyle at least once, wherein no additionalcomposition or heat is added.
 14. A method of manufacturing a reshapablehair styling composition comprising including in a hair stylingcomposition at least one (meth)acrylic copolymer comprising: (a) fromabout 20 to about 80 weight percent of units derived from ethyl hexyl(meth)acrylate, (b) from about 5 to about 65 weight percent of unitsderived from isobornyl (meth)acrylate, (c) from about 1 to about 15weight percent of units derived from acrylic acid, and (d) from about 1to about 15 weight percent of units derived from methacrylic acid,wherein the ratio of ethyl hexyl (meth)acrylate derived units toisobornyl (meth)acrylate derived units ranges from about 0.5:1 to about6:1; and wherein said at least one (meth)acrylic copolymer is present inan amount effective to provide a reshapable effect.